Hydrothermal method of manufacturing a novel catalytic material,catalysts containing said material,and processes using said catalysts

ABSTRACT

(A) HYDROTHERMAL CONVERSION METHOD FOR MANUFACTURING A NOVEL CATALYIC MATERIAL, COMPRISING A NOVEL SYNTHETIC LAYERED CRYSTALLINE CLAY-TYPE ALUMINOSILICATE MINERAL, PREFERABLY IN AN INTIMATED ADMIXTURE WITH AN AMORPHOUS COGEL COMPRISING SILICA AND ALUMINA, SAID MATERIAL BEING USEFUL AS A CATALYTIC CRACKING CATALYST AND AS A CRACKING COMPONENT OF A CATALYST CONTAINING AT LEAST ONE ADDITIONAL COMPONENT. SAID METHOD COMPRISING SUBJECTING TO CONDITIONS OF ELEVATED TEMPERATURE AND PESSURE A HYDORGEL OR HYDROGEL SLURRY, SAID SLURRY COMPRISING WATER, A COMPONENT SELECTED FROM FLUORINE AND COMPOUNDS OF FLUORINE, AND AN AMORPHOUS COGEL STARTING MATERIAL COMPRISING SILICA AND ALUMINA IN A SILICA/ALUMINA MOLAR RATIO ABOVE 3.3 UNTIL A SUBSTANTIAL AMOUNT OF SAID SYNTHETIC MINERAL IS FORMED, PREFERABLY IN AN INTIMATE ADMIXTURE WITH A SUBSTANTIAL AMOUNT OF UNREACTED AMORPHOUS COGEL COMPRISING SILICA AND ALUMINA; (B) THE NOVEL CATALYTIC MATERIAL SO MANUFACTURED, INCLUDING SAID SYNTHETIC MINERAL AS SUCH AND IN SAID INTIMATE ADMIXTURE WITH UNREACTED AMORPHOUS COGEL; (C) CATALYST COMPRISING SAID NOVEL CATALYTIC MATERIAL INCLUDNG CATALYST CONTAINING SAID SYNTHETIC MINERAL IN SAID INTIMATE ADMIXTURE WITH UNREACTED AMORPHOUS COGEL; AND (D) HYDROCARBON CONVERSION PROCESSES USING SAID CATALYSTS.

United States Patent O .No Drawing. Continuation-impart of applicationSer. No.

763,922, Sept. 30, 1968, now Patent No. 3,652,457. This application May19, 1970, Ser. No. 38,888 The portion of the term of the patentsubsequent to May 23, 1989, has been disclaimed Int. Cl. B01j 1/40; Cg11/02 U.S. Cl. 208-111 11 Claims ABSTRACT OF THE DISCLOSURE (a)Hydrothermal conversion method for manufacturing a novel catalyticmaterial, comprising a novel synthetic layered crystalline clay-typealuminosilicate mineral, preferably in an intmiate admixture with anamorphous cogel comprising silica and alumina, said material beinguseful as a catalytic cracking catalyst and as a cracking component of acatalyst containing at least one additional component, said methodcomprising subjecting to conditions of elevated temperature and pressurea hydrogel or hydrogel slurry, said slurry comprising water, a componentselected from fluorine and compounds of fluorine, and an amorphous cogelstarting material comprising silica and alumina in a silica/ aluminamolar ratio above 3.3, until a substantial amount of said syntheticmineral is formed, preferably in an intimate admixture with asubstantial amount of unreacted amorphous cogel comprising silica andalumina; (b) the novel catalytic material so manufactured, includingsaid synthetic mineral as such and in said intimate admixture withunreacted amorphous cogel; (c) catalysts comprising said novel catalyticmaterial, including catalysts containing said synthetic mineral in saidintimate admixture with unreacted amorphous cogel; and (d) hydrocarbonconversion processes using said catalysts.

RELATED APPLICATION This application is a continuation-in-part of JosephJatfe application Ser. No. 763,922, filed Sept. 30, 1968, and now U.S.Pat. 3,652,457.

INTRODUCTION This application relates to a novel catalytic materialcomprising an ovel synthetic layered crystalline clay-typealuminosilicate mineral, to a method for manufacturing said material, tocatalysts comprising said material, and to hydrocarbon conversionprocesses using said catalyst.

PRIOR ART It is known, particularly from Granquist U.S. Pat. 3,252,757,that a relatively new layered crystalline aluminosilicate clay-typemineral that has been synthesized has the empirical formula nSiO :Al OmABwcH O where the layer lattices comprise said silica, said alumina,and said B, and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F", OH",/2O and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

'ice

said mineral being characterized by a d spacing at said humidity withinthe range which extends from a lower limit of about 10.4 angstroms to anupper limit of about 12.0 angstroms when A is monovalent, to about 14.7angstroms when A is divalent, and to a value intermediate between 12.0angstroms and 14.7 angstroms when A ineludes both monovalent anddivalent cations. The equivalent of an exchangeable cation, A, in saidmineral, may be chosen from the group consisting of H+, NHJ, Li+, K/zCa' /aMg++, /2Sr++, and /zBa++, and mixtures thereof.

Said synthetic layered crystalline aluminosilicate mineral of saidGranquist patent is known from U.S. Pat. 3,252,- 889 to have applicationin calcined form as a component of a catalytic cracking catalyst, andapplications of said layered aluminosilicate in calcined form as acomponent of a hydrocracking catalyst have been disclosed in copendingapplications Ser. Nos. 760,619, now P.S. Pat. 3,535,228, and 750,038,now U.S. Pat. 3,535,233.

Said layered mineral of said Granquist patent is a randomlyinterstratified montmorillonite-mica, that is, one containing randomylalternating montmorillonite and mica layers. It expands upon glyceroltreatment, and ir reversibly collapses to a mineralogically differentmineral species upon calcination.

OBJECTS In view of the foregoing, it is an object of the presentinvention to provide a novel catalytic material of improvedcharacteristics, compared with the mineral of said Granquist patent,particularly for use as a component of a hydrocarbon conversioncatalyst, said material comprising a novel synthetic crystallineclay-type aluminosilicate, to provide a method for making said material,to provide catalysts comprising said material, and to providehydrocarbon conversion processes using said catalysts.

STATEMENT OF INVENTION In accordance with the method of the presentinvention, a hydrogel or hydrogen slurry comprising water, a componentselected from fluorine and compounds of fluorine, and an amorphous cogelstarting material comprising silica and alumina, said cogel startingmaterial having a silica/ alumina molar ratio above 3.3 and preferablybeing present in said hydrogel or hydrogel slurry in an amount of 5 to50 weight percent, preferably 5 to 25 weight percent, is subjected,preferably at a pH of 6 to 10, in a conversion zone to conditions ofelevated temperature and pressure, until a substantial amount ofcrystalline aluminosilicate mineral is formed, preferably in intimateadmixture with a substantial amount of unreacted cogel comprising silicaand alumina. Preferably the elevated temperature is in the range 170 to350 C. After the desired quantity of synthetic crystallinealuminosilicate mineral forms, said resulting slurry comprising saidmineral, preferably also comprising unconverted amorphous gel, is dried,to produce a catalytic material comprising said mineral, said catalyticmaterial being useful as a catalytic cracking catalyst or crackingcomponent of a catalyst containing at least one additional component.The desired quantity of crystalline mineral formed preferably is thatquantity which will result in 5 to weight percent, preferably 20 to 70weight percent, thereof in the final dried catalytic material. Saidmaterial, when it comprises said crystalline mineral in intimateadmixture with unreacted amorphous silica-alumina cogel, will have asurface area of 200 to 380 m. g. Said material, prior to or aftercalcining, may be impregnated with at least one catalytic hydrogenatingcomponent precursor to form a hydroprocessing catalyst. Said materialmay be calcined and used as such as a catalytic cracking catalyst, orcombined with other catalytic cracking components.

The synthetic layered crystalline clay-type aluminosilacate mineral ofthe present invention, that is formed by crystallization during theprocess of the present invention, has a silica-alumina ratio above 3.0.When that minoral, or the catalytic material referred to hereincomprising said mineral and unreacted amorphous cogel, is dried andcalcined, the d spacing of said mineral may be different than it wasprior to drying and calcining. However, said mineral, prior to dryingand calcining, has the following formula:

where the layer lattices comprise said silica, said alumina, and said B,and Where n is more than 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F OH '/2O- and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a d spacing at said humidity whichis between 10.25 angstroms and 10.4 angstroms when A is monovalent. Theequivalent of an exchangeable cation, in said mineral, may be chosenfrom the group consisting of H+, NH Li+, K /zBa++, /2Mg++, "/2 Sr++, and/zBa++, and mixtures thereof.

Preferably the hydrogel or hydrogel slurry is washed with diluteammonium acetate and Water before being subjected to the elevatedtemperature and pressure treatment of the process of the presentinvention.

The hydrogel or hydrogel slurry may be prepared in any convenientmanner, using suitable precursor compounds of the final components ofthe desired catalyst, and observing the silica/alumina ratios specifiedherein. A suitable general procedure for forming the hydrogel orhydrogel slurry may be found in Joseph Jaife US. Pat. 3,280,040.Aluminum-containing precursor compounds preferably are chlorides.Suitable silicon-containing pre cursor compounds are alkali metalsilicates. 1

Said catalytic hydrogenating component precursor com pound is selectedfrom compounds of nickel, cobalt, platinum, palladium and rhenuim. Inaddition to impregnation with said precursor compound, said materialcomprising said mineral advantageously may be impregnated with at leastone catalytic hydrogenating component precursor compound selected fromcompounds of tungsten, molybdenum, tin and zinc.

Any one or more of the elements contained in the aforementionedcatalytic hydrogenating component precursors may be present in a desiredfinal hydroprocessing catalyst, in the form of metals, oxides, sulfidesor any combination thereof, in amounts selected from the following list,based on the total catalyst, calculated as metals:

Element: Weight percent Ni or C 1-20 Pt or Pd 0.01-2.0

W or Mo 5-35 Sn or Zn 0.1-

the final catalyst, in the form of metals, oxides or sulfides,

are:

Ni or C0 Pt or Pd NiMo or CoMo NiW or CoW NiSn MoZn PtRe

PdRe

Said hydrogel or hydrogel slurry additionally may contain precursorcompounds of an oxide selected from titania, zirconia, hafnia, thoriaand ceria; any one or more of these oxides may be present in the finalcatalyst in an amount of 0 to 30 Weight percent.

Said hydrogel or hydrogel slurry should contain fluorine or a compoundof fluorine, in an amount which will provide fluorine or a compound offluorine in the final catalyst cracking component material in an amountof 0.1-3 weight percent, preferably 0.53 weight percent, more preferably0.5-2 weight percent, calculated as F.

Because the suitable hydrothermal conversion temperatures for formingthe desired synthetic crystalline mineral from precursors thereof liefar above the normal boiling point of water, the hydrogel or hydrogelslurry conveniently is subjected to said conditions at elevatedtemperature and pressure in a pressure vessel, so that the Watercontained therein will remain in the liquid state by autoclave action.The hydrogel or hydrogel slurry is maintained at the selectedtemperature and pressure for a suflicient period of time for theformation of the desired crystalline aluminosilicate to the desiredextent. Preferred temperatures are 340 to 700 F., at pressures above 500p.s.i.g., preferably above 900 p.s.i.g. The temperatures at which theformation of the desired crystalline aluminosilicate takes place is inthe practical range 530 to 700 F., with about 545 F. being optimum. Theoptimum temperature does not vary greatly with the presence in thehydrogel or hydrogel slurry of such final optional catalyst componentsas titania and zirconia. The pressure need not be appreciably in excessof the autoclave pressure of the hydrogel or hydrogel slurry, i.e., thatdeveloped by the vapor pressure of the water itself. The latter is onlynegligibly changed by the dissolved material in the hydrogel or hydrogelslurry, because the bulk of the solids therein is not in a formwhichappreciably changes the vapor pressure. Therefore, the ordinarytabulations of steam pressure may be used. Accordingly, at 545 F. thepressure developed is around 1000 p.s.i.g.

The reaction time may vary from 0.1 to hours, depending upon thereaction temperature, pressure and degree of conversion of the hydrogelor hydrogel slurry to said clay-type aluminosilicate that is desired.With lower reaction temperatures longer reaction times are required fora given degree of conversion, and vice versa. Preferably a reaction timeof 0.2 to 5 hours, more preferably 0.2 to 2 hours, is used.

When the hydrogel or hydrogel slurry has remained at the selectedconditions of temperature and pressure for a suflicient time for thedesired amount of the desired crystalline aluminosilicate to form, themixture is al lowed to cool, and the slurry containing said crystallinealuminosilicate is dried, for example at 200-450 F. Thereafter, thedried material may be calcined for use as a catalytic cracking catalyst,or may be combined prior to or after calcining with any desiredhydrogenation component or components to produce a hydroprocessingcatalyst. When a hydroprocessing catalyst is so produced, it preferablyis activated in an oxygen-containing gas stream, which may be air, at atemperature of 900 to 1150 F. for 0.5 to 20 hours, to produce the finalsolid catalyst. It has been found that optimum activity is developed inthesgatalyst if the activation temperatures does not exceed 11 F.

The hydroprocessing catalyst produced as described above may be used insuch reactions as hydrofining and hydrocracking. Those skilled in theart will recognize which catalytic components the catalyst shouldcontain for the particular reaction for which the catalyst will be used,and will be aware of the operating conditions at which the reactionshould be conducted.

As an alternative to using the novel catalytic material produced asdescribed above, in the manner described above, said material may bebroken into particles, for example pulverized into a powder, and saidparticles may be dispersed in a hydrogel or hydrogel slurry comprisingcomponents selected from precursor compounds of alumina, silica,silica-alumina, silica-alumina-titania, and silica-alumina-zirconia, andthe resulting mixture may be dried and activated, at the same conditionsused for drying and activating the material of said particles, to form acatalyst composite material. The hydrogel or hydrogel slurry in whichsaid particles are dispersed may contain any or all of the components ofthe hydrogel or hydrogel slurry used in making said particles, or maycontain any components that the foregoing discussion indicates couldhave been contained in the hydrogel or hydrogel slurry used in makingsaid particles. Additionally, the hydrogel or hydrogel slurry in whichsaid particles are dispersed may contain particles of crystallinezeolitic molecular sieve, preferably X or Y type. Said molecular sievedesirably may be an ultra-stable molecular sieve, that is, one having asodium content below 3 weight percent, calculated as Na O, a unit cellsize below about 24.65 angstroms, and a silica/alumina ratio above about2.15.

EXAMPLES The following examples will aid in understanding the catalystpreparation method of the present invention, and use of the catalystprepared thereby.

Example 1 Wt. percent of total cogelled material, anhy- Weight MolarComponent drous basis ratio ratio SiO2 67 AWL 33 2. 03/1 3.45 1

The amorphous cogelled precursor material is prepared by the followingsteps, using sufficient quantities of the starting materials to producethe above-indicated weight percentages of the components of saidcogelled precursor material.

(1) An aqueous acidic solution is prepared, containing AlCl and aceticacid.

(2) A dilute sodium silicate solution is added to said acidic solutionto form a clear dispersion of colloidal silica in AlCl and acetic acid.

(3) An ammonium hydroxide solution is added to said clear dispersion toprecipitate alumina and silica in the form of a hydrogel slurry, at a pHof 7-8.

(4) Ammonium bifiuoride is added to said hydrogel slurry, in an amountsuflicient to provide 0.1 to 3 weight percent fluoride in said hydrogelslurry, calculated as F, based on the silica and alumina in saidhydrogel slurry. Instead of ammonium bifiuoride, sodium fluoride or HFmay be used in preparation of the material of the present invention.

(5) The slurry is filtered to produce a hydrogel filter cake. The filtercake is partially dried to about 25% solids content and is extruded intosmall pellets. The pellets are washed repeatedly with dilute ammoniumacetate solution to remove sodium and chloride ionic impurities.

A slurry is formed from the washed hydrogel pellets and water, usingsufficient water to provide a slurry solids content of 10 wt. percent.The slurry is loaded into an autoclave and there is aged for 0.5 to 2hours at 1400 p.s.i.g. autogenous pressure (300 C.), resulting in aslurry containing a crystallized mineral, fluorine, and unreactedamorphous cogel, all in intimate admixture.

The autoclaved slurry is dried. X-ray diffraction and other examinationsof the resulting material indicate the presence of unreacted amorphouscogel, fluorine, and a synthetic. layered crystalline clay-typealuminosilicate, consisting predominantly of mica-like layers, all inintimate admixture. Upon treatment with glycerol the material does notswell, as does said Granquist synthetic aluminosilicate material.

Example 2 A portion of the material of Example 1 is calcined and used asa catalytic cracking catalyst.

Example 3 Another portion of the material of Example 1 is pulverized,moistened with a solution of palladium ammino nitnate and chromiumnitrate, extruded into Az-diameter pellets, dried and calcined to form ahydrocracking catalyst containing 0.5 weight percent palladium and 0.5weight percent chromium. Said catalyst is used to hydrocrack ahydrofined California gas oil of the following description:

Gravity, API 34 Aniline point, F. 193 Organic nitrogen, p.p.m. 0.1

Boiling range, F. 550-850 The hydrocracking conditions are as follows:

Liquid hourly space velocity, v./v./hr. 2.0 Per-pass conversion toproducts boiling below 400 F, vol. percent 60 Exit gas rate, s.c.f./bbl.5600 Total pressure, p.s.i.g 1200 The starting temperature necessary toachieve the indicated per-pass conversion is 580 F. The catalyst foulingrate is 0.025 F. per hour.

What is claimed is:

1. A hydrothermal conversion method for manufacturing a catalyticmaterial, said material comprising a layered crystalline clay-typealuminosilicate mineral, said aluminosilicate mineral prior to dryingand calcining having the formula nSiO A1 0 :mAB :xH O

where the layer lattices comprise said silica, said alumina, and said B,and where n is more than 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F OH, /2Oand mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a d spacing at said humidity whichis between 10.25 angstroms and 10.4 angstroms when A is monovalent, saidmethod comprising subjecting to conditions of elevated temperature andpressure in a reaction zone a hydrogel or hydrogel slurry, said slurrycomprising water, a component selected from fluorine and compounds offluorine, and an amorphous cogel material comprising silica and aluminain a silica/alumina molar ratio above 3.3, until a substantial amount ofsaid aluminosilicate mineral is formed.

2. The method as in claim 1, wherein said temperature is 170 to 350 C.

3. The method as in claim 1, with the additional steps of incorporatingin the reaction zone product a compononent comprising a hydrogenatingmetal, and drying and calcining the resulting composite to produce ahydrocarbon conversion catalyst.

4. The method as in claim 1, wherein said hydrogel or hydrogel slurry iswashed with dilute ammonium acetate and water before being subjected tosaid conditions of elevated temperature and pressure.

5. A synthetic layered crystalline clay-type aluminosilicate mineralwhich prior to drying and calcining has the following formula:

nSiO A1 mAB :xH O

where the layer lattices comprise said silica, said alumina, and said B,and where n is more than 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F-, 01-11/2O' and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a d spacing at said humidity whichis between 10.25 angstroms and 10.4 angstroms when A is monovalent.

6. The mineral of claim 5, in combination with a catalytic hydrogenatingcomponent.

7. An intimate admixture of the synthetic layered crystalline clay-typealuminosilicate mineral of claim 5, with an amorphous cogel materialcomprising silica and alumina.

8. The intimate admixture of claim 7, containing fluorine or a compoundof fluorine.

9. The intimate admixture of claim 7, in dried and calcined form,containing at least one hydrogenating component.

10. A slurry adapted to being dried to form a catalytic material,comprising a synthetic layered crystalline claytype mineral having asilica/ alumina ratio above 3.0, fluorine or a compound of fluorine, andunreacted amorphous silica-alumina cogel.

11. A hydrocarbon conversion process using as a catalyst the combinationof claim 6.

References Cited UNITED STATES PATENTS 3,252,757 5/1966 Granquist252-455 X 3,140,253 7/1964 Plank et a1. 252455 X 2,914,464 11/1959Burton et a1 208111 X CARL F. DEES, Primary Examiner US. Cl. X.R.252-442, 455 R

